Ernest augusts george street



UNIT D STATES PATENT OFFICE.

ERNEST AUGUsTE GEORGE STREET, o PARis, FRANCE.

IEXPLOSIVE AND METHOD OF MAKING SAME.

SPECIFICATION forming'part of Letters Patent No. 598,618, dated February 8, 18 98) Application filed September 7, 1897. Serial No. 650,836- (No sped-mm 7 in the following specification.

Being aware ofthe serious drawbacks met with in the manufacture, handling, and use of chlorate powders hitherto known in connection with explosives, I have endeavored to describe a method of obtaining stable explosives containing chlorat-es so that the ingredients, whatever be their sensitivenessto shock and temperature, may be thoroughly mixed withoutdanger.

The present invention relates, to such ex plosives and to the process of their manufacture. Ohlerate pewglers,likemlhexplosixes,

must consist of substances providing for combustion, ofthechlorate description, and of combustible substances,'the proportions beiug such that when explosion occurs a complete combustion takes place, (carbonic acid mixed with-each other.

sary to render the substances to be combined harmless under shocks and high temperatures 01 carbonic oxid.) It is necessary that the elements or ingredients constituting the explosive should be thoroughly combined or Finally, it is neceswhich mayoccurduring the manufacture and handlingof these explosives- I have found thatin orderto fulfil all these conditions it is necessary to render the combustible agent liquid during the whole process of manufacture. For this purpose I utilize the properties of certain oils to dissolve, when heated,nitro an dazo compounds, which I choose inpreference to all other combustible substances. Ifthe solubility of the nitro or azo compounds in these oils be small, I use other substances which are more soluble and are formed by the combination of two nitro compounds or of two azo w substance chosen.

compounds or of one nitro and one azo compound. 'I use, preferably, the exact quantity of oil required to dissolve the combustible The-oil itself plays the part of a'combus tible. But this quantity of oil must be sufiicient to preserve the fluidity of the combustible mixture during the whole process of the manufacture, and this must be i done in spite of the fact that the substance will have to be suitably heated. The oily coinbustible mixture surrounds each grain of chlorate, the element providing for combustion, 5 5 with a shell or coating of solid or paste-like combustible, so that when after the lgneadin g the mixture'is cooled there are formed crys-- tals of 'nitro or azo compounds around the grains of ,chlorate. I shell is proved by the .fact that in my explosives, having-for their bas'es,say, chlorate of soda, this'salt;usuallyhygrometrimis not in-- fluenced "byjatmosphericmoisture. It must: I also be pointedout that the oil cannot exude. 6 5 The mixture is preparedat a veryhigh temperature, so that when it is cooled and falls to the highest temperature occurring in sum' mer the crystallization or the paste-like state f 'is formed. The explosive obtained in this manner is so stable that it may be heated to to 200 centigradewithout its nature being in the least altered, and at the same time its effect when exploded is very powerful, owing to the combustible substances employed. 'These advantages disappear if chlo rate and the nitro or azo compound combustible are simply mixed together and the mixture moistened by oil and not dissolved in it as has been done with cold picric'acid. It is found that oil exudes when the temperature rises. Besides, it will be easily seen that by the simple mixing an explosive of less density is "obtained than when the material is dissolved in the oil. Before describing the details of manufacture of these chlorates it is necessary to give some details about the substances I have selected as combustible agentsin my explosives.

Nitro c0mp0unds.The nitro compounds, 0 which must not be confused with 'nitrated ethers, such as nitroglycerin" and nitrocellulose, are divided into nitrohydrocarbons, (mononitrobenzene, mononitronaphthalene, dinitronaphthalene, trinitronaphthalene, bi;-

.nitrobenzene, &c.,) nitrophenols, (trinitro phenols, picric acid,tetranitrodiphenols, &c'. and nitroamins, (nitroanilin, nitrated diphe- .nylamin, 850.) They are iusoluble. {or very slightly soluble in cold and hot mineral oils. Theyare little soluble in coldanimal-or vegetable oils, but are,'on the contrary, soluble in different proportions inthe latter category of oils if heated to a suitable temperature.

They existence of such 60 about 52.

The'following examples may be given: 1

h-ude mononitronaphthalene melts at siou-point is, 61?. .-At the ordinary'tempera-j in re (from to castor-oil dissolves about" twenty-five percent. of mononitronaphthalene-ethat is to saiy,'one hundred parts, by

weight, or "oil dissolve twenty-five parts. of mon-onitronaphthalene. From fifi i'p-pward this compound can be added in any propor tion.- The solubility in olive and linseed 'oil 1's practically the same as in castor-oi1;' A so-. luftion of equal parts of oil and amononl'ti o naphthalene solidifies when cooled.

Crude binitronaphthalenes,which are mixtures of binitronaphtlialenes A and B, the respectivem elting-points' being 240 and 170,

' are but slightly soluble in castor-oil. At the ordinary temperaturevscarcely one per cent.

dissolves. At 100 the solubility increases and.

At 125 the solubility becomes about sixty per cent,-

reaehes about four to five per cent.

while at the, melting temperature of the nitro conrpoundsilabout 170 to 18Q) the twoliquids-may. beuj ix'ed in any proportions, The solutionsolidifies when cooled.-

Crudebinitrobenzene,melts at about 7 0 an d 'ivhen' p ate at 909,; At the ordinary tempera-. ture its solubility in oastor-oil is about four per cent, in olive-oil about three per cent. and

-in linseed-oil about five per cent. At 90, thatemperature at which binitrobenzene is com} oil dissolves about fiv perjcent. of picric acid,

. zone,

caster-oil about four per cent, and olive-oil,

about one per cent. 'At 100 cast r-oildissolves about twentyper cent. of pieric acid,

'and at about 125 150 130, the temperature of fusion of picric acid, caster-oil does not dissolve more than fifty percent. of picric acid.

If a greaier' quantity isgalid'ed, the picric abid formsa brown liquidlayer under the oily so lution of picrio acid." I

' 20 compmmdssi have found, besides, that azo eompounds-azobenzol, azoxyben-- amidoazobenzol, diamidoazobenzol, dse.'--ha've the same properties'as nitro compounds. They are-much more soluble in anim al'andvegetable oils when heated than when cold and mostly insoluble or but little soluble in mineral oils even when'heated. Azobenzol and oxyazobenzol are, however, soluble in paraffin and Vaseline when heated. Amie doazobenzol and dia'midoazobenzol are less 1 in oils. It is also easyto produce these cont- Combinations of 'miro and azo compounds soluble.

bet-item themselvea-By studying nitro and ass compounds it willbe found that some of these substances are relatively little soluble 125 to 130 does not dissolve iuenstowoil to If purified and sublimatedtitsfu;v

oil.

a greater extent than fifty percent. These high temperatures cannot be used on a, large scale in the manufacture of powders, as they would in certain special cases be extremely dangerous: Besides, even by heating undersuch' conditions it will'be found impossible,

for instance, in the ease of picric acid to dissolve in the oili'a'isulfioientlquantity of it. To obviate'jthese drawbacks, I was led to study a whole class of'su'bstances produced by-the come dissolved in'oils at tern-peratureswhioh are muoh lgiwer their-those at'which their components dissolve. {the incorporation ofsuch combinative substances-in oil can there-:

fore be made without danger. It should be gcomb'ination of nitro onjazo compounds between. themselves, twoandtwo, in order to use them instead or nitro or azo compounds, which are little solublel inltheo oils. when heated. Thesoeomhinations meltv andrbee.

added thatby using. thesebinary combina tions much more powerful explosives are obtained-"than 'When their components-{the sing-1e nitro or azo compoundsbare employed.

'1. ese'binary eompou nds maybe prepared by the method generallyused in chemistry by combining the component's molecnle'to mole cule and in the state of fusion. I Kt firsttho substance is 'nglelted Whose temperature of fusionjs tlre fewest, and thenthe second sub stance isintroduc ed into the liquid mass. By

"combining a substance, comparatively spealging, veryfusible+such,' torlustance, asmouc rec nitronaphthalene+anda substance difficult to liquefy-sueh,-for instance, as picric acid a combination is produced themelting-point soluble. The combination takes place directly" in the oil. All the solutions of nitroco mpounds in oil can be, besides,obtained in this manner. Thus considerable quantities of,

combustible substances are incorporated in' hundred grams of pioric acid can be dissolved at whereas if three hundred and tortyfive grams of mononitronaphthalene have been previously dissolved in this kilogram of oil it will be afterward possible to dissolve at a temperature of 100 four hundred and fiftyfive grams of picric acid and at 125 six hundred and fort-y grams of mononitronaphthaleue and eight hundred and sixty grams of pioric acid. We will, however, examinoherer inaftcr in detail certain ofrtheso combinations Thus in one kilegram'of ononly five;

t ig

as regards their melting and their solubilitybinations of nitro or see compounds by dissolvingthe'componoutsullsiz'mces. in any solwith each other. Other oils behave very much to picronitronaphthalene. One kilogram of become possible to mix twenty grams of cas- "for picric acid.

- manufacture and melting-points and soluafter it has melted one kilogram three hundred- I have heated these solutions to 200;witho'ut bjlity of these binary combinations, which in my opinion are destined to play the chief part in the manufacture of chlorated; explosives.

As an example, in order to obtain picronitro naphthalene one kilogram of morionitronaphthalene is introduced into a vessel heated by a water-bath or by steam to or Then and twenty grams of picric acid is addedlittle by little. When the solution is compi'ete;'the whole is cast in plates. The combination is ready for use andmelts at 7el. Without heat caster-oil dissolves about five per cent. of this nitro combination. At 100 the solubility considerably increases, and casto-r-oil-can dissolve ninety per cent. of picronitronaphtha lene, which crystallizes when the solutionis cooled and solidified. Being heated to about 1O5 to-'110-, twenty grams of castor-oil can dissolve twenty, twenty-five, and even thirty grams of picronitronaphthalene. These two substances become capable of being mixed like castor oil. tacked when hot.

Picrobinitrobenzene is .prepared similarly Linseed-oil is slightly atbinitrobenzene and one'kilogram three hundred and sixty grams of picric acid are taken, the combination melting at 88.

- Castor-oil dissolves, when cold, six to seven per cent. of the combination--. At.lO0 --the solubility increases.

The oil can dissolve fifty per cent. of thenitro combination. By raising the temperature beyond 100 it will tor-oil and twenty grams 'of' p'icronitrobeuzene.-

Picrates of amidoazobenzol, azobenzid, azoxybenzid, and nitrodiphenylamins have practically the same solubility in oil as the azo compounds used for their preparation. Pi-

crate of diamidoazobenzol .is, h.owever, less .soluble than diamidoazobenzol only.

These picrate a'zo compounds are prepared by 'dis solving at first the azo compounds in oil at the temperature of 80 to 100and then add ingpicric acid in small portions. These solutions once prepared maybe heated to a point much higher than thatat which the azo compounds. decompose whenheate'd alone.

observing spontaneous decomposition br ex plosion. 1 v

Picramic acid can generally be'substituted.

New processes of manufacturing of 07110- kind of explosive, the nitro or the azo compound is dissolved inthe most suitable oil, heating it, if necessary, to the melting-point of the nitro compound as long as there isno danger of decomposition of the nitro compound or of explosion during this increase of temperature. The nitro compound or the azo mixed with the oily-solution.

compound must dissolve in such proportions,

that when cooled down to the highest summer temperatures it will crystallize, bringing aboutsolidification of the oily mass, or re- If it were found that dissolving un 'aration bythe-methods-indicated.:above, of.

the combination-.the'most soluble in oil of this nitro or azo compoundw'ith'another nitro or azo compound. Then, having obtained this binary compound it would be dissolved .in oil, as was the case for very soluble nitro com- "pounds; t The oily solution having been prepared, it is poured out into a stirring or mixing apparatus and heated toa suitable temtain perfect fluidity during the wholestirring operation. Then starch-orcarbon is added and stirred till it is thoroughly absorbed or Then finelypulverized alkaline chlorate or perchlorate is added little by little, the mass being cona liquid combustible is used, must continue till the mixture is very complete. Then it remains only to 'fill the catridges or to put up the material in the manner desired.

=Generallyspeaking, it is found that a good explosive should containabout ten to twenty per centfif oily solution obtained as hereinbefore described, eighty to sixty-five per cent. of; chlorate of an alkali, and ten to fifteen per cent. of fecula, starch, or carbon. The latter substances maybe dispensed with; but in such case the explosive should preferably be composed as follows: twenty to thirty per cent. of oily solution. and eighty to seventy per cent. of chlorate of an alkali.

IIC

The following are some examples which have been found to giveigood results:

Chlorate of potash, three kilograms; oily Chlorate of soda, seven hundred-and fiftygrams;- oily solution of pioronitronaphthalene, (in equal parts,) two hundred grams; starch, fifty grams.

, Chlorate-of soda, three hundred gramsg azobenzol, seve'nty grams; castor-oil, thirty grams.

Chlorate picroazobenzol, sixty grams; .castor-oil, forty grams. I

To the latter two mixtures may be added twenty to forty grams of starch.

Although perfect'fiuidity of the combustible nitro oraz'o' compound is necessary during the whole operation (consequent to the of potash, four-hundred grams;

A outhydrocarbons. IO

as the nitro bodies and are theequivalents.

, bustible agicntl'l do not restrict myself to two bodies onlyg previous solution) in order to obtain good ex plosives, I also reserve to myself the right to manufacture detonation mixtures by using eit ier nitro onazo compounds or binary combination formed by nitro and by azo coinpoundspreviouslywetted, when hot, by animal, vegetable, or mineral oil and afterward mixed With'an alkaline chlorate with or with- As simply wetting is employed in this case, mineral oil may be used W itho"ut inconvenience, as it is not intended I to dissolve the-combustible substance. I

It'has already been pointed out that the azo derivativespresent. the" same or similar characteristics for the'g'mrposes of this invention thereofl- LIt "Will hence be understoodv that where nitro'fderivatives are specified in the claims as ty ieal bodies the equivalent a zo bodiesare -td'. eiincluded. It will also be understood that tin forming a compound com- I claim- .1. The process of making explosives consisting in preliminarily dissolving in asuitable oil'at an elevated temperatureia combustible agent'snch as specifiedj.(such. as a nitro derivative) in such propcrtion'tha'toncooling-the oily mixture will assume by crystallization a pasty or solid consistence, and

then mixing with this solution alkaline'chlorate or perchlorateglmaintaining.the fluidity of the mass during v mialaaxation, substantiallyas described."--' v 1 2.' The process of making chlorate explosives consisting in combining a. less" soluble combustible agent with a more soluble coinbustible agent, dissolving this combination at an elevated temperature in a snitableoil,

in such ;'-proportion that on cooling the mix .ture assumes a solid or pasty condition'by crystallization, and then mixing with this solution the agentfsupporting combustion (ch10 rate or perchlorate) maintaining the fluidity of the mass during malaxation, substantially as described;

' 3. In .the,'manufac'tur. of explosives, the

p-rocesslof pr paring a, combustible solution.

for subseqne 't mixing-with the agent sup- .50 porting combustion, said process consisting in raising to a'high temperaturean oilwhich' is not asolventof nitroderivatiyesat ordinary temperature, and dissolvingii nitro derivative insaid heated oil in such proportion that,

on'cooling, the solution assumes by crystal- 4 lization a solid or-pasty condition, substan-Q l tia'lly as described.- I

4 The processof making chlorate explo 6O sives consisting in unitingat an elevated tern perature the selected combustible agent (as.

' a nitro orazo derivative or combination thereof) with an'oilwhich is not-a solvent thereof l at ordinary temperature,and mixing'the paste thus obtained-with the chlorate powder, substantially as described.- Y

5. An explosive whose combustibleelement is composed-of a solution of a nitro derivative in an-cilwh-ich is"notasolvenl thereofat ordinary temperature, substantially as (lescribed; v

6; An egg" I'losive-whose comb ustibleelement is compose of a solutionin oil of the coinbustiblefagent (such as a nitro derivative) in crystalline condition surrounding or coatingthe grains of the elementsnpportingcombustion.

7. An explosive v'hosecoinbustible elemen t is composed of a" solution in oil of a less soluble combustible body (such as-a nitro dc-.

rivative) combined with a more soluble body of the same class in crystalline condition, substantially as describe o 8. An explosive,whose combustible element EDWARD BARBARY.

presence of two subscrib- 

